Preparation of transition metal carboxylates

Abstract

This disclosure provides a process for making transition metal carboxylate compositions by combining in an polar aprotic first solvent a transition metal precursor and a Group 1 or Group 2 metal carboxylate under substantially acid-free and substantially anhydrous conditions, to generate a mixture comprising the transition metal carboxylate composition. Optionally, the transition metal carboxylate composition can be purified, for example, by substantially removing the first solvent provide a residue comprising the transition metal carboxylate composition, and also optionally, further by extracting the transition metal carboxylate composition from the residue with a non-coordinating second solvent to provide an extract comprising the transition metal carboxylate composition.

We claim: 
     
       1. A transition metal carboxylate composition produced by the process comprising;
 contacting under substantially anhydrous and substantially acid-free conditions
 1) a transition metal precursor having the formula [((M B ) y1 X x1 L l ) m ] q [C c ] m1 [A a ] m2  where
 M B  is a transition metal in the +x oxidation state where x is an integer from +1 to +6; each X independently is an anionic ligand having charge y where y is an integer from −3 to −1; 
 each L independently is a neutral ligand; 
 l is an integer from 0 to 7; 
 m is an integer from −4 to 4; 
 m =(y*x1)+(x*y1); 
 C is a cationic species having a charge c and c is an integer from +1 to +3; 
 A is an anionic species having a charge a and a is an integer from −1 to −3; 
 when m<0, |m*q|=c*m1 and m2=0; 
 when m=0, m1=0 and m=0; and 
 when m>0, m*q=|a*m2| and m1=0, 
 
 2) a Group 1 or Group 2 metal C 3 -C 25  carboxylate, and 
 3) a first solvent 
 to form a transitio metal carboxylate 
 wherein M B  is Cr and 
 wherein the transition metal carboxylate is characterized as having a KBr pellet infrared spectrum with a υ asym  (CO 2 ) peak infrared absorption peak within 110 cm −1  of the υ sym  (CO 2 ) infrared absorption peak and having an infrared absorbance peak height ratio of a υ asym  (CO 2 ) infrared absorption peak at 1516±15 cm −1  to infrared absorbance peak located at 700±50 cm −1  greater than or equal to 3:1. 
 
 
     
     
       2. The composition of  claim 1  , wherein the transition metal precursor has the formula M B X X,L   l  where M B  is Cr in the x oxidation state and x is an integer from 1 to 6; each X independently is a monoanionic ligand; each L independently is a neutral ligand; and l is an integer from 0 to 7. 
     
     
       3. The composition of  claim 1 , wherein each X independently is a halide, nitrate, sulfate, or phosphate and each L independently is a C 2 -C 40  ether, a C 2 -C 40  thioether, a C 2 - C 20  nitrile, a C 1 -C 60  amine, a C 3 -C  60  phosphine, or any combination thereof. 
     
     
       4. The composition of  claim 1 , wherein the Group  1  or Group 2 metal carboxylate has the formula (M A ) q [(O 2 C) r R 1c ] s  where M A  is a Group 1 or Group 2 metal; (O 2 C) t R 1c  is a C 3 - C 25  carhoxylate where r is an integer from 1 to 4 and R 1c  is a hydrocarbon group or a substituted hydrocarbon group; q is r divided by the greatest common divisor of r and the oxidation state of M A ; and s is the oxidation state of M A  divided by the greatest common divisor of r and the oxidation state of M A . 
     
     
       5. The composition of  claim 1 , wherein the Group 1 or Group 2 metal carboxylate has the formula M A O 2 CR 2c  where M A  is a Group 1 metal, O 2 CR 2c  is a C 3 -C 25  monocarboxylate, and R 2c  is a hydrocarbyl group or a substituted hydrocarbyl group. 
     
     
       6. The composition of  claim 1 , wherein the carboxylate of the transition metal carboxylate composition comprises a monocarboxylate having a formula  − O 2 CR 2c wherein R 2c  is hydrocarbyl group or a substituted hydrocarbyl group. 
     
     
       7. The composition of  claim 1 , therein the transition metal precursor and Group 1 or Group 2 metal carboxylate are contacted at a carboxylate group to transition metal equivalent ratio from 095:1 to 1.3:1. 
     
     
       8. The composition of  claim 1 , wherein the first solvent comprises a C 2 -C 40  ether, a C 2 -C 40  thioether, a C 2 -C 20  nitrile, a C 1 -C 60  amine, a C 3 -C 60  phosphine, or any combination thereof. 
     
     
       9. The composition of  claim 1 , wherein the transition metal precursor has a formula CrX 3 L l  where
 each X independently is a halide, 
 each L independently is a C 2 -C 10  ether, a C 2 -C 10  thioether, a C 2 -C 5  nitrile, a C 1 -C 30  amine, or a C 3 -C 30  phosphine, or any combination thereof, and 
 l ranges from 0 to 7, and 
 the Group 1 or Group 2 metal carboxylate is a Group 1 metal C 3 -C 25  monocarboxylate. 
 
     
     
       10. The composition of  claim 9 , wherein the carboxylate of the Group 1 metal carboxylate comprises a propionate, a butyrate, a pentanoate, a hexanoate, heptanoate, an octanoate, a nonanoate, a decanoate, undecanoate, dodecanoate a tridecanoate, a tetradecanoate, a pentadecanoate, a hexadecanoate, a heptadecanoate , an octadecanoate, or any combination thereof. 
     
     
       11. The composition of  claim 9 , wherein the carboxylate of the Group  1  metal car boxylate comprises 2-ethylhexanoate. 
     
     
       12. The composition of  claim 9 , wherein the transition metal precursor having the formula CrX 3 L 3  and the Group 1 metal carboxylate are contacted at a Group 1 metal carboxylate to chromium molar ratio from 3:1to 3.6:1. 
     
     
       13. The composition of  claim 9 , wherein the first solvent comprises a C 2 -C 40  ether, a C 2 -C 40  thioether, a C 2 -C 20  nitrile , a C 1 -C 60  amine, or a C 3 -C 60  phosphine, or any combination thereof. 
     
     
       14. The composition of  claim 9 , further comprising evaporating the first solvent from the mixture to provide the transition metal carboxylate composition. 
     
     
       15. The composition  claim 14 , further comprising purifying the transition metal car boxy late composition by contacting the first transition metal car boxylate composition with a non-coordinating solvent to form a solution, filtering the solution, and evaporating the non-coordinating solvent to provide a purified transition metal carboxylate composition. 
     
     
       16. A chromium(III) carboxylate composition characterized as having a KBr pellet infrared spectrum with a υ asym  (CO 2 ) peak infrared adsorption peak within 110 cm −1  of the υ sym  (CO 2 ) infrared adsorption peak and having an infrared absorbance peak height ratio of a υ asym  (CO 2 ) infrared absorbance peak at 1516±15 cm −1  to infrared absorbance peak located at 700±50 cm −1  greater than or equal to 3:1. 
     
     
       17. The chromium(III) carboxylate composition of  claim 16 , wherein the KBr pellet infrared spectrum has an infrared absorbance peak height ratio of an infrared absorbance peak at 1516±15 cm −1  to an infrared absorbance peak at 1429±15 cm −1  greater than or equal to 0.5:1. 
     
     
       18. The chromium(III) carboxylate composition  claim 16 , wherein the KBr pellet infrared spectrum has an infrared absorbance peak height ratio of a υ sym (CO 2 ) infrared absorbance peak located at 1616±20 cm −1  to a υ asym  (CO 2 )infrared absorbance peak at 1429±15 cm −1  less than or equal to 0.8:1. 
     
     
       19. The chromium(III) carboxylate composition of  claim 16 , wherein the KBr pellet infrared spectrum has an infrared absorbance peak height ratio of a υ sym  (CO 2 ) infrared absorbance peak located at 1429±15 cm −1  to a υ asym  (CO 2 ) infrared absorbance peak at 1685±20 cm −1  greater than or equal to 3.5:1. 
     
     
       20. The chromium( III) carboxylate composition of  claim 16 , wherein the carboxylate chromium(III) carboxylate composition comprises a C 3  to C 25  carboxylate. 
     
     
       21. The chromium(III) carboxylate composition of  claim 16 , wherein the carboxylate of chromium(III) carboxylate composition comprises a propionate, a butyrate, a pentanoate, a hexanoate, a heptanoate, an octanoate, a nonanoate, a decanoate, undecanoate, a dodecanoate, a tridecanoate, a tetradecanoate, a pentadecanoate, a hexadeeanoate, a heptadecanoate, an octadecanoate, or any combination thereof. 
     
     
       22. The chromium(III) carboxylate composition of  claim 16 , wherein the carboxylate of chromium(III) carboxylate composition comprises 2-ethyl hexanoate. 
     
     
       23. A chromium(III) car boxylate composition haying a goodness of fit test value, R 2 , of at least 0.6 when comparing high-energy X-ray diffraction g(r) data points of the chromium(III) carboxylate composition to a calculated high energy X-ray diffraction g(r) data points of a theoretical model of mononuclear chromium(III) acetate over an r range from 1.3 Angtroms to 4 Angstroms. 
     
     
       24. The chromium(III) carboxylate composition of  claim 23 , wherein the goodness of fit test value R 2 =1−(SS err /SS tot ), where
 1) SS err the summation of the squares of the residual between the high energy X-ray diffraction g(r) data points of the chromium(III) carboxylate composition and the high energy X-ray diffraction g(r) data points for the calculated high energy X-ray diffraction g(r) of a theoretical model of mononuclear chromium(III) acetate over the range of 1.3 Angstroms to 4 Angstroms, and 
 2) SS tot  is the summation of the squares of the differences between the high energy X-ray diffraction g(r) data points of the chromium(III) carboxylate composition and the mean of the high energy X-ray diffraction g(r) data points of the chromium(III) carboxylate composition over the range of 1,3 Angstroms to 4 Angstroms. 
 
     
     
       25. The chromium(III) carboxylate composition of  claim 23 , wherein the goodness of fit test value, R 2 , is calculated using a optimized fit between the high-energy X-ray diffraction g(r) data points of the chromium(III) carboxylate composition and the calculated high energy X-ray diffraction g(r) data points of a theoretical model of mononuclear chromium(III) acetate are optimized over the r range of 1.3 Angstroms to 4 Angstroms, the optimized being achieved by
 1) converting calculated high energy X-ray diffraction d(r) data points for the theoretical model of mononuclear chromium(III) acetate model to the high energy X-ray diffraction g(r) data points and scaling the calculated high energy -ray diffraction g(r) data points of the theoretical model of the mononuclear chromium(III) acetate model to the chromium(III) carboxylate composition over the r range of 1.3 Angstroms to 4 Angstroms using the equation g(r)=((((d(r)/(4π*ρ 0 *r))+1)*fac)+C) where ρ 0 , fac, and C are scaling variables, by 
 2) minimizing the sum of the squared differences between the calculated high energy X-ray diffraction g(r) data points for the mononuclear chromium(III) acetate model and the high energy X-ray diffraction g(r) data points of the chromium(III) carboxylate composition over the r range of 1.3 Angstroms to 4 Angstroms using the scaling variables ρ 0 , fac, and C with the constraint calculated high energy X-ray diffraction g(r) data points of the theoretical model of mononuclear chromium(III) acetate at r=1.79 Angstroms is equal to 0. 
 
     
     
       26. The chromium(III) carboxylate composition of  claim 23 , wherein the high-energy X-ray diffraction g(r) data points of the chromium(III) carboxylate composition and the calculated high energy X-ray diffraction g(r) data points of a theoretical model of mononuclear chromium(III) acetate utilized to calculate the goodness of fit test value are provided at intervals of 0.01 Angstorms. 
     
     
       27. The chromium(III) carboxylate composition of  claim 23 , wherein carboxylate of chromium(III) carboxylate composition comprises a C 3  to C 25  carboxylate. 
     
     
       28. The chromium(III) carboxylate composition of  claim 23 , wherein the carboxylate of chromium(III) carboxylate composition comprises a propionate, a butyrate, a pentanoate, a hexanoate, a heptanoate, an octanoate, a nonanoate, a decanoate, an undecanoate, a dodecanoate, as tridecanoate, a tetradecanoate, a pentadecanoate, a hexadecanoate, a heptadecanoate, an octadecanoate, or any combination thereof. 
     
     
       29. The chromium(III) carboxylate composition of  claim 23 , wherein the carboxylate of chromium(III) carboxylate composition comprises 2-ethylhexanoate. 
     
     
       30. A process for preparing a transition metal carboxylate composition comprising:
 contacting under substantially anhydrous and substantially acid-free conditions
 1) a transition metal precursor having the formula [((M B ) y1 X x1 L l ) m ] q [C c ] m1 [A a ] m2  where
 M B  is a transition metal in the +x oxidation state where x is an integer from +1 to +6; each X independently is an anionic ligand having charge y where y is an integer from −3 to −1; 
 each L independently is a neutral ligand; 
 l is an integer from 0 to 7; 
 m is an integer from −4 to 4; 
 m=(y*x1)+(x*y1); 
 C is a cationic species having a charge c and c is an integer from +1 to +3; 
 A is an anionic species having a charge a and a is an integer from −1 to −3; 
 when m<0, |m*q|=c*m1 and m2=0; 
 when m=0, m1=0 and m=0; and 
 when m>0, m*q=|a*m2| and m1=0, 
 
 2) a Group 1 or Group 2 metal C 3 -C 25  carboxylate, and 
 3) a first solvent 
 
 to form a transition metal carboxylate. 
 
     
     
       31. The process of  claim 30 , wherein the transition metal precursor has the formula M B X x L l  where M B  is a transition metal in the x oxidation state and x is an integer from 1 to 6; each X independently is a monoanionic ligand; each L independently is a neutral ligand; and l is an integer from 0 to 7. 
     
     
       32. The process of  claim 30 , wherein M B  is Ti, Zr, V, Nb, Cr, Mn, Fe, Co or Cu. 
     
     
       33. The process of  claim 30 , wherein each X independently is a halide, nitrate, sulfate, or phosphate and each L independently is a C 2 -C 40  ether, a C 2 -C 40  thioether, a C 2 -C 20  nitrile, a C 1 -C 60  amine, a C 3 -C 60  phosphine, or any combination thereof. 
     
     
       34. The process of  claim 30 , wherein the Group 1 or Group 2 metal carboxylate has the formula (M A ) q [(O 2 C) r R 1c ] s  where M A  is a Group 1 or Group 2 metal; (O 2 C) r R 1c  is a C 3 -C 25  carboxylate where r is an integer from 1 to 4 and R 1c  is a hydrocarbon group or a substituted hydrocarbon group; q is r divided by the greatest common divisor of r and the oxidation state of M A ; and s is the oxidation state of M A  divided by the greatest common divisor of r and the oxidation state of M A . 
     
     
       35. The process of  claim 30 , wherein the Group 1 or Group 2 metal carboxylate has the formula M A O 2 CR 2c , M A  is a Group 1 metal, O 2 CR 2c  is a C 3 -C 25  monocarboxylate, and R 2c  is a hydrocarbyl group or a substituted hydrocarbyl group. 
     
     
       36. The process of  claim 30 , wherein the carboxylate of the transition metal carboxylate composition comprises a monocarboxylate having a formula  − O 2 CR 2c  wherein R 2c  is hydrocarbyl group. 
     
     
       37. The process of  claim 30 , wherein the transition metal precursor and Group 1 or Group 2 metal carboxylate are contacted at an equivalent ratio of carboxylate groups to transition metal oxidation state from 0.95:1 to 1.3:1. 
     
     
       38. The process of  claim 30 , wherein the first solvent comprises a C 2 -C 40  ether, a C 2 -C 40  thioether, a C 2 -C 20  nitrile, a C 1 -C 60  amine, a C 3 -C 60  phosphine, or any combination thereof. 
     
     
       39. The process of  claim 30 , further comprising evaporating the first solvent to provide the transition metal carboxylate composition. 
     
     
       40. The process  claim 30 , further comprising purify the transition metal carboxylate composition by contacting the transition metal carboxylate composition with a non-coordinating solvent to form a solution, filtering the solution, and evaporating the non-coordinating solvent to provide a purified transition metal carboxylate composition. 
     
     
       41. The process of  claim 30 , further comprising 1) contacting the transition metal carboxylate composition with a chlorosilane and a solvent to form a mixture, 2) allowing the mixture to sit for a period of time, 3) filtering the mixture to remove any precipitate, 4) evaporating the solvent to provide a purified transition metal carboxylate composition. 
     
     
       42. The transition metal carboxylate composition of  claim 1 , wherein the KBr pellet infrared spectrum has an infrared absorbance peak height ratio of a υ sym (CO 2 ) infrared absorbance peak at 1516±15 cm −1  to an infrared absorbance peak at 1429±15 cm −1  greater than or equal to 0.5:1. 
     
     
       43. The transition metal carboxylate composition of  claim 1  , wherein the KBr pellet infrared spectrum has an infrared absorbance peak height ratio of a υ sym (CO 2 ) infrared absorbance peak located at 1616±20 cm −1  to a υ asym (CO 2 ) infrared absorbance peak at 1429±15 cm −1  less than or equal to 08:1. 
     
     
       44. The transition-metal carboxylate composition of  claim 1 , wherein the KBr pellet infrared spectrum has an infrared absorbance peak height ratio of a υ sym (CO 2 ) infrared absorbance peak located at 1429±15 cm −1  to a υ asym  (CO 2 ) infrared absorbance peak at 1685±20 cm −1  greater than or equal to 3.5:1. 
     
     
       45. The chromium(III) carboxylate composition of  claim 16  having a goodness of fit test value, R 2 , of at least 0.6 when comparing high-energy X-ray diffraction g(r) data points of the chromium(III) carboxylate composition to a calculated high energy X-ray diffraction g(r) data points of a theoretical model of mononuclear chromium(III) acetate over an r range from 1.3 Angstroms to 4 Angstroms. 
     
     
       46. The chromium(III) carboxylate composition of  claim 16 , wherein the goodness of fit test value R 2 =1−(SS err /SS tot ), where
 1) SS err =the summation of the squares of the residual between the high energy X-ray diffraction g(r) data points of the chromium(III) carboxylate composition and the high energy X-ray diffraction g(r) data points for the calculated high energy X-ray diffraction g(r) of a theoretical model of mononuclear chromium(III) acetate over the range of 1.3 Angstroms to 4 Angstroms, and 
 2) SS tot  is the summation of the squares of the differences between the high energy X-ray diffraction g(r) data points of the chromium(III) carboxylate composition and the mean of the high energy X-ray diffraction g(r) data points of the chromium(III) carboxylate composition over the range of 1.3 Angstroms to 4 Angstroms. 
 
     
     
       47. The chromium(III) carboxylate composition of  claim 16 , wherein the goodness of fit test value, R 2  is calculated using a optimized fit between the high-energy X-ray diffraction g(r) data points of the chromium(III) carboxylate composition and the calculated high energy X-ray diffraction g(r) data points of a theoretical model of mononuclear chromium(III) acetate are optimized over the r range of 1.3 Angstroms to 4 Angstroms, the optimized being achieved by
 1) converting calculated high energy X-ray diffraction d(r) data points for the theoretical model of mononuclear chromium(III) acetate model to the high energy X-ray diffraction g(r) data points and scaling the calculated high energy X-ray diffraction g(r) data points of the theoretical model of the mononuclear chromium(III) acetate model to the chromium(III) carboxylate composition over the r range of 1.3 Angstroms to 4 Angstroms using the equation g(r)=((((d(r)/(4π*ρ 0 *r)) +1)*fac)+C) where ρ 0 , fac, and C are scaling variables, by 
 2) minimizing the sum of the squared differences between the calculated high energy X-ray diffraction g(r) data points for the mononuclear chromium(III) acetate model and the high energy X-ray diffraction g(r) data points of the chromium (III) carboxylate composition over the r range of 1.3 Angstroms to 4 Angstroms using the scaling variables ρ 0 , fac, and C with the constraint calculated high energy X-ray diffraction g(r) data points of the theoretical model of mononuclear chromium(III) acetate at r=1.79 Angstroms is equal to 0. 
 
     
     
       48. The chromium(III) carboxylate composition of  claim 16 , wherein the high-energy X-ray diffraction g(r) data points of the chromium(III) carboxylate composition and the calculated high energy X-ray diffraction g(r) data points of a theoretical model of mononuclear chromium(III) acetate utilized to calculate the goodness of fit test value are provided at intervals of 0.01 Angstorms.